The titlecomplex [Ag(carbene)2]2[Ag2Br4] has been synthesized by the reaction of Ag2O with 1-ethyl-3-benyl-imidazolium bromide in DMSO at room temperature, and characterized by elemental analysis, 1H NMR and single-crystal X-ray diffraction analysis. It crystallizes in triclinic, space group Pīwith a = 10.1597(10), b =11.0646(11), c = 13.0245(14) Å, α = 102.230(2), β = 90.606, γ = 113.9250(10)o, V = 1300.3(2) Å3, Mr= 748.06, Z = 2, Dc = 1.911 g/cm3, µ(MoKα)= 4.60 mm-1 and F(000) = 728. The structure was refined to R = 0.0316 and wR = 0.0835 for 3744 observed reflections with I > 2σ(I). The title compound crystallizes as a cen- trosymmetric tetranuclear compound. One half of the molecule comprises the asymmetric unit of the structure. The Ag(1) atom is nearly linear or T-shaped when the Ag(1)–Ag(2) interaction is taken into consideration, which is bi-coordinated by two carbene carbon atoms. The Ag(2) atom adopts tetrahedral geometry. The catalytic behavior of the title complex has been investigated, and the results indicate it has a highly catalytic activation for L-lactide polymerization.